DE916733C - Process for the preparation of polymerization products - Google Patents

Description

Issued on the basis of the First Overhead Line Act of July 8, 1949

(WiGBI. P. 17S)

FEDERAL REPUBLIC OF GERMANY

ISSUED AUGUST 16, 1954

GERMAN PATENT OFFICE

PATENT LETTERING

CLASS 39 c GROUP 25 oi

D 5148 IVc] ₃₉ C

Dr. Hellmut Bredereck and Dipl.-Chem. Erich Bäder, Stuttgart

have been named as inventors

German gold and silver refinery formerly Roessler, Frankfurt / M. and W. C. Heraeus G. m. b. H., Hanau / M.

Process for the manufacture of polymerization products

Addition to patent 913 477. Patented in the territory of the Federal Republic of Germany from August 1, 1950

The main patent started on July 18, 1950

Patent application known since October 29, 1953

Patent granted July 8, 1954

The invention relates, like that of the main patent, to a process for the production of Polymerization products of unsaturated organic compounds, such as unsaturated hydrocarbons, Vinyl compounds, acrylic compounds, styrenes or allyl compounds, in the presence of polymerization catalysts to lower the polymerization temperature and to increase the rate of polymerization.

According to the patent 913 477 as a polymerization accelerator nitrogen-containing compounds of the arylsulfonic or alkanolamine type are used, in which at least one hydrogen atom on

Nitrogen through a radical of the general formula

R '

R-SO ₉

R "

is replaced, in which R is any organic, in particular aliphatic, aromatic, hydroaromatic or heterocyclic hydrocarbon radical and R 'and R "denote hydrogen or an optionally substituted hydrocarbon radical, where

R, R 'and R "can be identical and R' and R" can be closed to form a ring.

It has now been found that the polymerization of polymerizable organic compounds can be achieved with a doubly bonded terminal methylene group then particularly quickly and at particularly low temperatures can be carried out if one after or in place of the amines the patent 913,477 analogous compounds of the general formula

R-SO ₀ -C-R '

R "

used. In this formula, R denotes an optionally substituted hydrocarbon radical, in particular an aliphatic, aromatic, hydroaromatic or heterocyclic radical. R 'represents a radical which has a loosening effect on the hydrogen atom on the carbon atom. Such radicals are primarily the hydroxyl group and its derivatives OR '", in which R'" denotes an alkyl or acyl radical. The corresponding sulfur compounds, that is to say the residues of mercaptans or thioethers, can also be used. R "denotes hydrogen or an optionally substituted hydrocarbon radical such as R; R" can, however, also denote a radical which has an activating effect on the hydrogen atom, such as R 'or a sulfone-containing radical R-SO ₂ -CH. If R 'and R "contain hydrocarbon radicals, they can also be closed to form a ring.

The process according to the invention is applicable to the same compounds to be polymerized as the procedure of the main patent. As polymerization catalysts for these compounds Arylsulfoncarbinols are expediently according to the invention the general formula

R - C ₆ H ₄ - SO ₂ - C - OH R "

for example benzene- or p-toluene-sulfone-carbinol the formula

respectively.

r ₁ - S 0 "- C Ho - OH

CH ₃ - C ₆ H ₄ - SO ₂ - CH ₂ - OH

or their mixtures with amines according to the main patent, e.g. B. Benzene- or p-toluene-sulfon-methyl- (dinexyl) -amine, used. However, it is also possible to use compounds in which the carbinol radical is substituted by other hydrocarbon radicals in addition to the arylsulfone radical, e.g. B. Benzenesulfone or p-toluene-sulfone-methyl-carbinol of the following formula

C ^ ₅ -SO ₂ -CH-OH

CH *

CH ₃ - C ₀ H ₄ - SO ₂ - CH - OH

CH,

As in the main patent, polymerization accelerators according to the invention can be used in addition and, if applicable, those of the main patent also further known polymerization catalysts, in particular those of the oxygen-containing type can be used.

The same polymerization processes as in the main patent can be used, and it may be particularly useful to polymerize the liquid or dissolved monomers or partially polymerized compounds in the presence of already polymerized portions of the same compound perform.

The polymerization products produced by the new process can be used in the areas of the main patent, depending on the application with those listed in the main patent Additives can be added. In particular, the polymerization products for Production of varnishes, adhesives and paints, fillers, impregnation compounds, sealing compounds, Heat, sound and electricity insulation materials, model and impression compounds are used will. The new polymers are also used with particular preference in the field of prosthetics, especially in the dental field.

For this purpose, polymerization approaches are advantageously used to carry out the process, the one hand from the liquid or dissolved to be polymerized monomer or partially polymerized Compound and on the other hand consist of a preferably powdered polymer, the up must be stored separately for polymerization. The polymerisation catalysts according to the invention can be used as the liquid portion contain, while the powdery portion may contain the oxygen-containing Contains polymerization catalyst. But you can also use the catalysts of the invention add powdery portion, also in addition to the oxygen-containing catalyst.

example

To test the inventively proposed polymerization 1 ecm monomeric methyl methacrylate is in each case with 3 g of the same polymeric ester, the 4 ° / ₀ dibenzoyl peroxide and 2 ° / contains ₀ of the polymerization according to the invention, stirred to form a slurry and, even of 35 °, the other Starting from room temperature, polymerizes until it hardens.

The following polymerization accelerators were used:

1. Phenyl-sulfone-carbinol
C ₆ H ₅ -SO ₂ -CH ₂ OH

2. p-Tolyl-sulfon-carbinol
CH ₃ - C ₆ H ₄

3. p-Tolyl-sulfone- (methyl) -carbinol

SO ₂ - CH ₂ OH

CH ₃ -C ₆ H ₄ -SO ₂ -CH (OH) -CH ₃

4. p-Tolyl-sulfone ~ (propyl) -carbinol

CH ₃ -C ₆ H ₄ -SO ₂ -CH (OH) -CH ₂ -CH ₀ -CH ₃

5. p-Tolyl-sulfon- (propenyl) -carbinol

CH ₃ -C ₆ H ₄ -SO ₂ -CH (OH) - CH = CH -CH ₃

6. p-Chlorophenyl-sulfone-carbinol P-Cl-C ₆ H ₄ -SO ₂ -CH ₂ OH

7. Octylsulfon-propyl-carbinol
C ₈ H ₁₇ -SO ₂ -CH (OH) -C ₃ H ₇

8. Dodecylsulfonic carbinol
^ 12 25 * ^ C * ₂ - CH ₂ OH

9. Dodecylsulfonpropylcarbinol C ₁₂ H ₂₅ -SO ₂ -CH (OH) -C ₃ H ₇

These polymerization accelerators, some of which are new compounds, were produced according to the method of Meyer (Journ. for practical chemistry, vol. 63, p. 167 [1901]) and by E. P. Kohler and M. Reimer (Am. Formerly J., Vol. 31, Pp. 165 to 167 [1904]).

The results of the polymerization with these accelerators can be found in the following table:

Polymerization Polymerization time in minutes Dei /.lmmer-
temperature accelerator at 3 ₅ ° 12th I. 5 12 to 14 2 5 to 6 - 3 IO 10 to 12 4th 4th - 5 4 to 5 - 6th 7th 18th 7th - 8th 6 to 8 - 9 6 to 8

The products obtained are notable for the fact that they have no discoloration whatsoever and are excellent Hardness and complete absence of bubbles have properties that the new catalysts Issue polymers, even if in addition to them known catalysts of the various chemical Compositions are used and these are critical to the acceleration of the polymerization.

Claims (3)

Patent claims: i. Further training of the manufacturing process of polymerization products from polymerizable compounds with a double bonded terminal methylene group according to Patent 913 477, characterized in that in addition to or instead of the amines mentioned there as polymerization accelerators compounds of the general formula R-SO ₂ -C-R ' R " can be used in which R is an optionally substituted hydrocarbon radical, in particular an aliphatic, aromatic, hydroaromatic or heterocyclic radical, R 'is a radical, such as OH or OR'", which has a loosening effect on the hydrogen atom on the carbon atom, R" is hydrogen, an optionally substituted carbon hydrogen radical, such as R, or a radical that has an activating effect on the hydrogen atom on the carbon atom, such as R ', or a sulfone-containing radical R-SO ₂ -CH and R'"is an alkyl or acyl radical. 2. The method according to claim 1, characterized in that that as a polymerization accelerator Arylsulfoncarbinole of the general formula H
R - C ₈ H _d - SO "- C - OH R " be used. 3. The method according to claims 1 and 2, characterized in that it is carried out with Polymerization batches, consisting of the liquid or dissolved monomer to be polymerized or partially polymerized compound which optionally contains the polymerization accelerator 100. according to claim 1 or 2 contains, on the one hand, and a preferably powdered polymer the monomeric compound containing the oxygen-containing polymerization catalyst, preferably but also according to claim 1 or 2, contains, on the other hand. © 9538 8.